Reverse Differential Pulse Voltammetry and Polarography

In this paper we obtain the analytical solution for the reverse Werential pulse O P ) technique for a slow electronic transfer process, starting fkom expressions obtained previously for the faradaic response to a triple potential pulse. The solutions are valid for the planar approximations of a static mercury drop electrode and of a dropping mercury electrode. An irreversible reduction process gives rise in the RDP technique to the appearance of two peaks, one at more negative potentials than the normal reduction potential, E", and the other at more positive potentials than E". From half-width peak and peak potential measurements, it is possible to evaluate approximately the kinetic and thermodynamic parameters corresponding to the electronic transfer, such as the transfer coefficient, a, the normal reduction potential, E", and the apparent heterogeneous rate constant, k,. The solutions are checked against experimental examples of well-known processes.